阅读说明：本技术 改性三氧化钼的制备方法、聚烯烃复合材料及其制备方法 (Preparation method of modified molybdenum trioxide, polyolefin composite material and preparation method thereof ) 是由 黄家奇 刘凯 齐亮 汤灏 于 2019-11-27 设计创作，主要内容包括：本发明公开一种改性三氧化钼的制备方法、聚烯烃复合材料及其制备方法,涉及高分子复合材料技术领域。所述改性三氧化钼的制备方法包括以下步骤：将LaCl<Sub>3</Sub>·6H<Sub>2</Sub>O加入乙醇溶液中,充分搅拌,得LaCl<Sub>3</Sub>溶液备用；在30～50℃水浴加热条件下,将三氧化钼加入浓硝酸溶液中反应2～4h,分离洗涤后,真空干燥,得中间体；将所述中间体加入所述LaCl<Sub>3</Sub>溶液中浸泡1～3h,真空干燥,即得到所述改性三氧化钼。将三氧化钼用稀土溶液表面改性,大大提高了其在共混物中的分散性,将其加入到聚烯烃复合材料中,对聚烯烃的结晶有诱导作用,能够促使聚烯烃异相成核,从而使得聚烯烃的结晶更加完整,提高了聚烯烃复合材料的强度、抗形变等性能。(The invention discloses a preparation method of modified molybdenum trioxide, a polyolefin composite material and a preparation method thereof, and relates to the technical field of polymer composite materials. The preparation method of the modified molybdenum trioxide comprises the following steps: adding LaCl 3 ·6H 2 Adding O into the ethanol solution, and fully stirring to obtain LaCl 3 The solution is ready for use; adding molybdenum trioxide into a concentrated nitric acid solution to react for 2-4 hours under the water bath heating condition of 30-50 ℃, separating and washing, and then performing vacuum dryingDrying in air to obtain an intermediate; adding the intermediate to the LaCl 3 And soaking the solution for 1-3 hours, and drying in vacuum to obtain the modified molybdenum trioxide. The molybdenum trioxide is surface modified by rare earth solution, so that the dispersibility of the molybdenum trioxide in the blend is greatly improved, and the molybdenum trioxide is added into the polyolefin composite material, has an induction effect on polyolefin crystallization, and can promote polyolefin heterogeneous nucleation, so that the polyolefin crystallization is more complete, and the strength, the deformation resistance and other properties of the polyolefin composite material are improved.)

1. The preparation method of the modified molybdenum trioxide is characterized by comprising the following steps:

adding LaCl₃·6H₂Adding O into the ethanol solution, and fully stirring to obtain LaCl₃The solution is ready for use;

under the water bath heating condition of 30-50 ℃, adding molybdenum trioxide into a concentrated nitric acid solution for reaction for 2-4 h, separating and washing, and then drying in vacuum to obtain an intermediate;

adding the intermediate to the LaCl₃And soaking the solution for 1-3 hours, and drying in vacuum to obtain the modified molybdenum trioxide.

2. The method of claim 1, wherein the LaCl is added to the mixture₃·6H₂Adding O into the ethanol solution, and fully stirring to obtain LaCl₃In the step of preparing a solution, the LaCl₃·6H₂The mass ratio of O to the ethanol solution is (20-30): (240-280).

3. The method for preparing the modified molybdenum trioxide according to claim 1, wherein in the step of adding molybdenum trioxide into a concentrated nitric acid solution for reaction for 2-4 hours under the water bath heating condition of 30-50 ℃, separating and washing the mixture, and then drying the mixture in vacuum to obtain the intermediate, the drying in vacuum is performed for 1-3 hours at 40-60 ℃.

4. The method of claim 1, wherein the intermediate is added to the LaCl₃And soaking the solution for 1-3 hours, and drying in vacuum to obtain the modified molybdenum trioxide, wherein the drying in vacuum is carried out for 1-3 hours at the temperature of 30-50 ℃.

5. The method of claim 1, wherein the intermediate is added to the LaCl₃Soaking in the solution for 1-3 h, and vacuum drying to obtain the intermediate and the LaCl₃The mass ratio of the solution is (40-60): (280-320).

6. The polyolefin composite material is characterized by comprising the following raw materials in parts by weight:

80-100 parts of polyolefin and 2-4 parts of modified molybdenum trioxide;

wherein the modified molybdenum trioxide is produced by the method for producing a modified molybdenum trioxide according to any one of claims 1 to 5.

7. The polyolefin composite of claim 6, further comprising the following parts by weight of raw materials: 0.1-0.5 part of antioxidant.

8. Polyolefin composite according to claim 6, wherein the polyolefin is any of PP, PE, PET, PBT and PA 6.

9. The polyolefin composite of claim 7, wherein said antioxidant is at least one of Irganox168, Irganox1010, and Irganox 1330.

10. A process for the preparation of a polyolefin composite according to any of claims 6 to 9, characterized in that it comprises the following steps:

mixing 80-100 parts of polyolefin, 2-4 parts of modified molybdenum trioxide and 0.1-0.5 part of antioxidant, and uniformly stirring to obtain a mixture;

and putting the mixture into an extruder for extrusion granulation to obtain the polyolefin composite material.

Technical Field

The invention relates to the technical field of polymer composite materials, and particularly relates to a preparation method of modified molybdenum trioxide, a polyolefin composite material and a preparation method thereof.

Background

Polyolefin is an important thermoplastic material and is widely applied to the fields of automobiles, household appliances, mechanical parts, office supplies, communication equipment and the like. The polyolefin has the advantages of light weight, no toxicity, no odor, good water absorption and the like. However, with the increasing use of polyolefin materials, in some specific material application fields, there are higher requirements for the physical properties of polyolefin, such as high strength and deformation resistance, and the ordinary polyolefin materials can not meet the requirements.

Disclosure of Invention

The invention mainly aims to provide a preparation method of modified molybdenum trioxide, a polyolefin composite material and a preparation method thereof, and aims to provide a polyolefin composite material with excellent performance.

In order to achieve the purpose, the invention provides a preparation method of modified molybdenum trioxide, which comprises the following steps:

adding LaCl₃·6H₂Adding O into the ethanol solution, and fully stirring to obtain LaCl₃The solution is ready for use;

under the water bath heating condition of 30-50 ℃, adding molybdenum trioxide into a concentrated nitric acid solution for reaction for 2-4 h, separating and washing, and then drying in vacuum to obtain an intermediate;

adding the intermediate to the LaCl₃And soaking the solution for 1-3 hours, and drying in vacuum to obtain the modified molybdenum trioxide.

Optionally, the step of contacting the LaCl₃·6H₂Adding O into the ethanol solution, and fully stirring to obtain LaCl₃In the step of preparing a solution, the LaCl₃·6H₂O and BThe mass ratio of the alcoholic solution is (20-30): (240-280).

Optionally, in the step of adding molybdenum trioxide into a concentrated nitric acid solution to react for 2-4 hours under the water bath heating condition of 30-50 ℃, separating and washing, and then drying in vacuum to obtain the intermediate, the drying in vacuum is performed for 1-3 hours at 40-60 ℃.

Optionally, said adding said intermediate to said LaCl₃And soaking the solution for 1-3 hours, and drying in vacuum to obtain the modified molybdenum trioxide, wherein the drying in vacuum is carried out for 1-3 hours at the temperature of 30-50 ℃.

Optionally, said adding said intermediate to said LaCl₃Soaking in the solution for 1-3 h, and vacuum drying to obtain the intermediate and the LaCl₃The mass ratio of the solution is (40-60): (280-320).

The invention further provides a polyolefin composite material, which comprises the following raw materials in parts by weight:

80-100 parts of polyolefin and 2-4 parts of modified molybdenum trioxide;

wherein the modified molybdenum trioxide is prepared by the preparation method of the modified molybdenum trioxide.

Optionally, the polyolefin composite material further comprises the following raw materials in parts by weight: 0.1-0.5 part of antioxidant.

Optionally, the polyolefin is any one of PP, PE, PET, PBT and PA 6.

Optionally, the antioxidant is at least one of Irganox168, Irganox1010 and Irganox 1330.

The invention further provides a preparation method of the polyolefin composite material, which comprises the following steps:

mixing 80-100 parts of polyolefin, 2-4 parts of modified molybdenum trioxide and 0.1-0.5 part of antioxidant, and uniformly stirring to obtain a mixture;

and putting the mixture into an extruder for extrusion granulation to obtain the polyolefin composite material.

According to the preparation method of the modified molybdenum trioxide, the polyolefin composite material and the preparation method thereof, the molybdenum trioxide is subjected to surface modification by using the rare earth solution, so that the dispersibility of the molybdenum trioxide in a blend is greatly improved, the molybdenum trioxide is added into the polyolefin composite material, the modified molybdenum trioxide has an induction effect on polyolefin crystallization, and the polyolefin heterogeneous nucleation can be promoted, so that the polyolefin crystallization is more complete, and the physical properties of the polyolefin composite material, such as strength, deformation resistance and the like, are improved.

Drawings

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.

FIG. 1 is a schematic flow chart of an embodiment of a method for preparing modified molybdenum trioxide according to the present invention;

FIG. 2 is a schematic flow chart of an embodiment of a method for preparing a polyolefin composite material according to the present invention.

The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

It should be noted that those whose specific conditions are not specified in the examples were performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Polyolefin is an important thermoplastic material and has the advantages of light weight, no toxicity, no odor, good water absorption and the like. However, with the increasing use of polyolefin materials, in some specific material application fields, there are higher requirements for the physical properties of polyolefin, such as high strength and deformation resistance, and the ordinary polyolefin materials can not meet the requirements. In view of the above, the invention provides a preparation method of modified molybdenum trioxide, a polyolefin composite material and a preparation method thereof. As shown in fig. 1, the preparation method of the modified molybdenum trioxide comprises the following steps:

s11, adding LaCl₃·6H₂Adding O into the ethanol solution, and fully stirring to obtain LaCl₃The solution is ready for use.

In this step of the present invention, LaCl is added₃·6H₂The mass ratio of the O (lanthanum trichloride hexahydrate) to the ethanol solution is (20-30): (240 to 280) may be, for example, 20:240, 25:260, 26:270, 28:280, 30:280 or the like, and the modified molybdenum trioxide obtained in the above range is most effective.

In addition, in the present example, the ethanol solution was used to disperse the LaCl₃·6H₂O (lanthanum trichloride hexahydrate) is dissolved, so the concentration of the ethanol solution is not limited by the invention as long as LaCl can be dissolved₃·6H₂O (lanthanum trichloride hexahydrate) can be dissolved.

S12, adding molybdenum trioxide into a concentrated nitric acid solution to react for 2-4 h under the water bath heating condition of 30-50 ℃, separating and washing, and drying in vacuum to obtain an intermediate.

In the step, the separation and washing are preferably carried out until the pH value of the molybdenum trioxide is 7, so that the nitric acid on the surface of the molybdenum trioxide is completely washed. The vacuum drying condition is drying for 1-3 h at 40-60 ℃, so that the surface performance of the molybdenum trioxide can be ensured.

S13, adding the intermediate to the LaCl₃And soaking the solution for 1-3 hours, and drying in vacuum to obtain the modified molybdenum trioxide.

In the step, the preferable vacuum drying condition is drying at 30-50 ℃ for 1-3 h, and the low-temperature vacuum drying is favorable for modifying the surface of the molybdenum trioxide. Furthermore, intermediates and said LaCl₃The mass ratio of the (lanthanum trichloride) solution is (40-60): (280-320) can be 40:280, 45:310, 50:300, 55:290, 60:320 and the like.

The invention further provides a polyolefin composite material, which comprises the following raw materials in parts by weight:

80-100 parts of polyolefin and 2-4 parts of modified molybdenum trioxide, wherein the modified molybdenum trioxide is prepared by the preparation method of the modified molybdenum trioxide.

According to the invention, the molybdenum trioxide is subjected to surface modification by using a rare earth solution lanthanum trichloride solution, so that the dispersibility of the molybdenum trioxide in a blend is greatly improved, the molybdenum trioxide is added into a polyolefin composite material, and the modified molybdenum trioxide has an induction effect on polyolefin crystallization and can promote polyolefin heterogeneous nucleation, so that the polyolefin crystallization is more complete, and the physical properties such as strength, deformation resistance and the like of the polyolefin composite material are improved.

Preferably, 0.1-0.5 part of antioxidant is added into the polyolefin composite material to prevent the polyolefin composite material from aging and prolong the service life of the polyolefin composite material. The type of the antioxidant is not limited in the present invention, and preferably, in this embodiment, the antioxidant is at least one of Irganox168 (antioxidant 168), Irganox1010 (antioxidant 1010) and Irganox1330 (antioxidant 1330), and the antioxidant has high antioxidant capacity, good compatibility with polyolefin, no precipitation, and good processability; it is non-volatile and non-decomposed at the processing temperature of the high polymer, and has low price, thus reducing the cost of the polyolefin composite material.

The invention is not limited to the type of the polyolefin, and preferably, in this embodiment, the polyolefin is any one of PP (polypropylene), PE (polyethylene), PET (polyethylene terephthalate), PBT (polybutylene terephthalate) and PA6 (nylon 6), and the polyolefin has wide application in industry, is a common polymer material, and is optimized to facilitate the utilization of the advantages thereof, thereby further increasing the application range thereof.

The present invention further provides a method for preparing a polyolefin composite material as described above, referring to fig. 2, the method for preparing the polyolefin composite material comprises the following steps:

s10, mixing 80-100 parts of polyolefin, 2-4 parts of modified molybdenum trioxide and 0.1-0.5 part of antioxidant, and uniformly stirring to obtain a mixture.

S20, putting the mixture into an extruder to extrude and granulate, and obtaining the polyolefin composite material.

Preferably, in the step, the extruder is a twin-screw extruder, the twin-screw extruder can improve efficiency and reduce cost, and the obtained polyolefin composite material has uniform particles and best performance.

The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.